TWI664251B - Uv可固化塗料組合物，其塗佈方法及經其塗覆的基材 - Google Patents

Uv可固化塗料組合物，其塗佈方法及經其塗覆的基材 Download PDF

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TWI664251B
TWI664251B TW106146553A TW106146553A TWI664251B TW I664251 B TWI664251 B TW I664251B TW 106146553 A TW106146553 A TW 106146553A TW 106146553 A TW106146553 A TW 106146553A TW I664251 B TWI664251 B TW I664251B
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coating composition
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polyurethane acrylate
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後補後補
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中國大陸商Ppg塗料(天津)有限公司
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Abstract

本發明提供一種高硬度耐鋼絲絨性UV可固化塗料組合物，其包含高官能度UV可固化聚胺基甲酸酯丙烯酸酯。本發明進一步提供一種用高硬度耐鋼性UV可固化塗料組合物塗覆基材之方法及經其塗覆之基材。

Description

UV可固化塗料組合物，其塗佈方法及經其塗覆的基材
本發明係關於一種具有耐指紋性、高耐鋼性及高硬度之UV可固化塗料組合物，且尤其係關於一種包含高官能度UV可固化聚胺基甲酸酯丙烯酸酯之UV可固化塗料組合物。本發明進一步係關於一種用該UV可固化塗料組合物塗覆基材之方法及經其塗覆之基材。
與傳統塗料相比，UV可固化塗料之優勢係物理及化學特性及裝飾效能，且因此已廣泛塗佈於聚甲基丙烯酸酯(PMMA)/聚碳酸酯(PC)/聚對苯二甲酸乙二酯(PET)基材上，以賦予此類基材包括耐指紋性、高耐鋼性及高硬度之特性。當前UV可固化塗料組合物展現不佳耐鋼特性，其主要由鋼絲絨測試前後接觸角之明顯差異反映。因此，需要具有改良之耐指紋性、高耐鋼性及高硬度的UV可固化塗料組合物。
本發明提供一種UV可固化塗料組合物，其包含官能度大於或等於6之UV可固化聚胺基甲酸酯丙烯酸酯。 本發明進一步提供一種於基材上形成塗層之方法，其包含將UV可固化塗料組合物塗佈至基材之至少一部分，其中該UV可固化塗料組合物包含官能度大於或等於6之UV可固化聚胺基甲酸酯丙烯酸酯。 本發明進一步提供一種經塗覆基材，其包含基材及沈積於基材之至少一部分上之UV可固化塗料組合物，其中該UV可固化塗料組合物包含官能度大於或等於6之UV可固化聚胺基甲酸酯丙烯酸酯。
出於以下詳細描述之目的，除非其中明確地相反指定，否則應瞭解本發明可採用各種替代性變化形式及步驟順序。此外，除任何操作實例中或以其他方式指示外，說明書及申請專利範圍中用於表達例如成分數量之所有數值理解為在所有情況下藉由術語「約」修飾。因此，除非有相反指示，否則以下說明書及隨附申請專利範圍中所闡述之數值參數為近似值，其可視本發明待獲得之所需特性而變化。最低限度地，且不試圖將均等論(doctrine of equivalents)之應用限於申請專利範圍之範疇，各數值參數至少應根據所報導之有效數位之數目且藉由應用一般捨入技術來解釋。 儘管闡述本發明之廣泛範疇的數值範圍及參數係近似值，但儘可能精確地報導特定實例中所闡述之數值。然而，任何數值均固有地含有因其對應測試量測值中發現之標準差所必然引起的某些誤差。 另外，應瞭解本文中所述之任何數值範圍皆意欲包括其中包含之所有子範圍。舉例而言，「1至10」之範圍意欲包括所述最小值1與所述最大值10之間(且包括最小值1及最大值10)的所有子範圍，亦即具有等於或大於1之最小值及等於或小於10之最大值。 在本申請案中，除非另外特定陳述，否則使用單數包括複數且複數涵蓋單數。另外，在本申請案中，除非另外特定陳述，否則使用「或」意謂「及/或」，儘管「及/或」可明確地用於某些情況。此外，在本申請案中，除非另外特定陳述，否則使用「一(a/an)」意謂「至少一種(個)」。舉例而言「一」成膜樹脂、「一」交聯有機粒子、「一」無機顏料粒子及其類似者係指此等物品中任一者之一或多者。 除非特定陳述為一個參考物，否則如說明書及隨附申請專利範圍中所用，冠詞「一」及「該」包括多個參考物。 本發明係針對提供一種具有耐指紋性、高耐鋼性及高硬度之塗料組合物，其係UV可固化的。UV固化之優勢係諸如固化時間短、設備簡單、能量利用高及對環境無傷害，且因此其廣泛用於塗層、印記、交聯劑及結構性材料之快速固化。UV固化尤其適用於電子消費者產品之表面塗層。 UV固化塗料組合物包含高官能度UV可固化聚胺基甲酸酯丙烯酸酯。聚胺基甲酸酯丙烯酸酯通常藉由使多異氰酸酯、多元醇及丙烯酸羥基酯反應來製備。因為聚胺基甲酸酯丙烯酸酯含有胺基甲酸酯及丙烯酸酯官能基，所以固化時形成之塗層將具有藉由聚胺基甲酸酯貢獻之高抗刮擦性、可撓性、高撕裂強度及低溫特性，及藉由聚丙烯酸酯貢獻之極佳光學特性及耐候性。可用於本發明中之聚胺基甲酸酯丙烯酸酯寡聚物可為脂族聚胺基甲酸酯丙烯酸酯寡聚物及芳族聚胺基甲酸酯丙烯酸酯寡聚物。脂族聚胺基甲酸酯丙烯酸酯寡聚物較佳，因為其具有優良可撓性及光穩定度，且不易變黃。 可用於本發明中之脂族聚胺基甲酸酯丙烯酸酯之數量平均分子量(Mn)較佳係800-4000。數量平均分子量(Mn)藉由凝膠滲透層析法使用諸如聚苯乙烯標準物之適當標準物來測定。 此外，可用於本發明中之脂族聚胺基甲酸酯丙烯酸酯之官能度較佳大於或等於6。藉由使用此類高官能度聚胺基甲酸酯丙烯酸酯形成之塗層在硬度、鋼絲絨、物理特性上表現良好，展現包括耐磨性高及鋼絲絨測試後之接觸角變化小之優勢。 舉例而言，可用於本發明中之脂族聚胺基甲酸酯丙烯酸酯可選自由以下組成之群：六官能度脂族聚胺基甲酸酯丙烯酸酯、七官能度脂族聚胺基甲酸酯丙烯酸酯、八官能度脂族聚胺基甲酸酯丙烯酸酯、九官能度脂族聚胺基甲酸酯丙烯酸酯、十官能度脂族聚胺基甲酸酯丙烯酸酯及其混合物。 舉例而言，可用於本發明中之脂族聚胺基甲酸酯丙烯酸酯可包含六官能度脂族聚胺基甲酸酯丙烯酸酯、十官能度脂族聚胺基甲酸酯丙烯酸酯或其混合物。較佳地，根據本發明之UV可固化聚胺基甲酸酯丙烯酸酯包含以塗料組合物之重量計約5-50 wt%之六官能度脂族聚胺基甲酸酯丙烯酸酯及約5-50 wt%之十官能度脂族聚胺基甲酸酯丙烯酸酯。 六官能度脂族聚胺基甲酸酯丙烯酸酯可為異佛爾酮二異氰酸酯及新戊四醇三丙烯酸酯之反應產物。十官能度脂族聚胺基甲酸酯丙烯酸酯可藉由異佛爾酮二異氰酸酯單體聚合得。 許多市售脂族聚胺基甲酸酯丙烯酸酯皆可用於本發明中。舉例而言，可用於本發明中之此類脂族聚胺基甲酸酯丙烯酸酯之實例包括(但不限於)來自Wuxing之W4560、來自Lida之U-0672-100、來自DSM之2421、來自Changxing之6195-100、來自Mitsui之RA4800M、來自Lihua之U-0930及其類似物。 根據本發明之UV可固化塗料組合物進一步包含以塗料組合物之重量計1-3 wt%之光引發劑。對於所用光引發劑並無特定限制，只要其在暴露於光輻射時可分解以產生自由基且起始光聚合反應即可。可用光引發劑包括(但不限於)安息香衍生物、二苯基乙二酮縮酮衍生物、二烷氧基苯乙酮、α-羥烷基苯基酮、α-胺基烷基苯基酮、醯基膦氫化物、酯化肟酮化合物、芳基過氧化物酯化合物、鹵甲基芳基酮、含有機硫化合物、苯甲醯基甲酸酯及其類似物。可視需要選擇兩種或更多種光引發劑。 許多市售光引發劑皆可用於本發明中。舉例而言，可用於本發明中之此類光引發劑之實例包括(但不限於)來自Taiwan DBC之DBC184/TPO/BP/200、來自Ciba之184/TPO/BP/MBF及其任何組合。 根據本發明之UV可固化塗料組合物進一步包含有機溶劑。對於所用溶劑並無特定限制，其可為熟習此項技術者已知之有機溶劑中之任一者且其包括(但不限於)脂族或芳族烴，諸如Solvesso 100TM 、甲苯或二甲苯；醇，諸如丁醇或異丙醇；酯，諸如乙酸乙酯、乙酸丁酯或乙酸異丁酯；酮，諸如丙酮、甲基異丁基酮或甲基乙基酮；醚、醚-醇或醚酯，諸如3-乙氧基丙酸乙酯，或前述中之任一者之混合物。其較佳為乙酸乙酯及/或乙酸異丁酯及/或甲基乙基酮。溶劑之量通常係第二塗料組合物之10-50 wt%。 根據本發明之UV可固化塗料組合物進一步包含一或多種其他添加劑，其包括(但不限於)防污染劑、分散劑、調平劑、抗氧化劑、消泡劑、流變劑及其類似物。此等添加劑之類型為熟習此項技術者所熟知，且其量將容易視需要由熟習此項技術者確定。 較佳地，UV可固化塗料組合物包含以塗料組合物之重量計0.1-3 wt%之含氟丙烯酸防污劑，其與高官能度UV可固化聚胺基甲酸酯丙烯酸酯一起用以增強所得塗層之耐指紋性及耐磨性。此類防污劑之實例包括(但不限於)來自ShinEtsu之KY-1203。 根據本發明之UV可固化塗料組合物可藉由此項技術中已知之技術塗佈於基材之至少一部分上，其包含例如噴霧、輥軋、簾式塗佈、浸漬/浸沒、刷塗或流動塗覆。接著，所得塗料膜經受UV固化，其可例如藉由在60-80℃下焙烤5-10分鐘以蒸發溶劑，之後在400-1600 mJ/cm2 之UV能量及80-300 mW/cm2 之光強度下UV照射來達成。塗層之薄膜厚度通常在5至10 μm之範圍內。 可將根據本發明之UV可固化塗料組合物塗佈至任何基材。該基材可包括(但不限於)陶瓷、木材、皮革、石頭、玻璃、合金、紙、塑膠、纖維、棉織物及其類似物，較佳係塑膠基材。塑膠基材尤其係指電子產品之電子顯示器，諸如機載顯示器、行動電話之PET保護膜及電腦之顯示器。塑膠基材可由聚甲基丙烯酸酯(PMMA)、聚碳酸酯(PC)及聚對苯二甲酸乙二酯(PET)製備。 實例 提供以下實例以說明本發明，然而其不應視為限制本發明之細節。除非另外指明，否則以下實例中以及本說明書通篇中之所有份數及百分比皆以重量計。 製備實例 根據本發明之UV可固化塗料組合物藉由混合表1中所列之組分及其量來製備。 表1.UV可固化塗料組合物之配方 1 六官能度脂族聚胺基甲酸酯丙烯酸酯，來自Wuxing之W45602 十官能度脂族聚胺基甲酸酯丙烯酸酯，來自Lida之U-0672-1003 溶劑：乙酸丁酯及乙酸異丁酯之混合物4 Irgacure 184，Taiwan DBC5 KY1203，Xinyue 塗層之製備製程 塗料組合物用藉由以適當比率混合乙酸乙酯、異丙醇及乙二醇單丁醚調配之稀釋劑來稀釋，以使得塗料組合物在稀釋後之黏度係7.5-8.5s，其中黏度係經由IWATA 2號杯量測。接著，經稀釋塗料組合物經由噴霧、簾式塗佈、輥軋、浸漬/浸沒塗覆中之任一者而塗覆於PMMA/PC/PET基材上，之後在60-80℃下焙烤5-10分鐘以移除溶劑。光引發劑經由暴露於UV光輻射(UV能量：400-1600 mJ/cm2 ，光強度：80-300 mw/cm2 )分解以產生活性自由基且起始單體與樹脂之間的聚合反應，從而形成三維交聯網路膜，以獲得底塗層。 接著，測試經本發明之UV可固化塗料組合物塗覆之基材之以下特性。結果顯示於表2中。 測試條目 1.鉛筆硬度 對鉛筆之要求：選擇Mitsubishi 4H鉛筆及1000號砂紙。鉛筆尖與砂紙平面呈90º之角度，且接著將其磨成圓柱形。 測試方法. 將鉛筆安裝於鉛筆硬度測試儀上，進行校準，調節至平衡，且負載1 kg之重量。在感測器之指紋感測表面之不同位置以45±1之角度切割5-10 mm長度之三條線。接著，用橡皮擦除鉛筆刮痕。 注意：在刮擦一次之後旋轉鉛筆90度以避開鉛筆尖之磨損區域，否則，測試結果無效。 2. 抗刮擦性 使用BONSTAR 0000號鋼絲絨，其中負載係1000 g，且鋼絲絨面積係20 mm×20 mm。測試在60個循環/分鐘之速率下進行，其中摩擦距離係35-40 mm。對樣品之蓋板之經膜塗覆之表面進行2000次連續摩擦。在鋼絲絨測試之後需要接觸角大於90。 3.固化膜之黏著力 樣品表面用NT刀以6×6條線切割(1 mm²柵格(晶格)，總數25個；標記一直穿透至基材)且測試表面保持儘可能平坦(保持刀片鋒利)。若樣品太小而不具有足夠的交叉切割空間，則將獲得45°橫切柵格。將Nichiban膠帶(第405號)、Scotch膠帶(第610號)或相同類型之其他膠帶(18 mm寬，膠帶黏度應大於或等於5.3 N/18mm寬度)施用於樣品表面上且用橡膠壓實以使得膠帶與樣品表面充分接觸。將樣品靜置3分鐘。膠帶藉由以90º角度背向膠帶本身將其快速拉掉來移除。目測檢查測試表面且參看ISO標準進行評定。 ISO標準分級 0級：5B 切口邊緣完全平滑，且在晶格之邊緣無剝離發生。 1級：4B 在切口交叉點有一小片剝離，且實際破壞小於或等於5%。 2級：3B 在切口邊緣或交叉點有剝離，剝離面積5%至15%。 3級：2B 沿切口邊緣有部分剝離或大片剝離，或一部分晶格整體剝掉，剝離面積在15%-35%之範圍內。 4級：1B 在切口邊緣有許多剝離，或一些晶格部分或全部剝掉，剝離面積在35%-65%之範圍內。 5級：0B 在切口之邊緣或交叉點塗漆剝掉明顯，剝離面積大於65%。 需要測試結果處於或高於4B。 4. 水接觸角 使用市售接觸角測試儀。需要初始接觸角大於105。 5.透射率測試 測試程序根據WI-SOP-164 ＜光學透射率量測儀＞進行。對於透明材料，需要透射率大於90º。 表2.效能測試結果 儘管上文已解釋且描述了本發明之特定態樣，但對熟習此項技術者應顯而易見的是，可對本發明作出許多變化及修改而不偏離本發明之範疇及精神。因此，隨附申請專利範圍意欲涵蓋屬於本發明之此等變化及修改。

Claims (9)

  1. 一種UV可固化塗料組合物，其包含官能度大於或等於6之UV可固化聚胺基甲酸酯丙烯酸酯，其中該UV可固化聚胺基甲酸酯丙烯酸酯包含以該塗料組合物之重量計5-50wt%之六官能度脂族聚胺基甲酸酯丙烯酸酯及5-50wt%之十官能度脂族聚胺基甲酸酯丙烯酸酯。
  2. 如請求項1之UV可固化塗料組合物，其中該UV可固化聚胺基甲酸酯丙烯酸酯之數量平均分子量係800至4000。
  3. 如請求項1之UV可固化塗料組合物，其中該六官能度脂族聚胺基甲酸酯丙烯酸酯係異佛爾酮二異氰酸酯及新戊四醇三丙烯酸酯之反應產物。
  4. 如請求項1之UV可固化塗料組合物，其中該十官能度脂族聚胺基甲酸酯丙烯酸酯係藉由異佛爾酮二異氰酸酯單體聚合得。
  5. 如請求項1之UV可固化塗料組合物，其進一步包含以該塗料組合物之重量計0.1-3wt%之含氟丙烯酸防污劑。
  6. 一種於基材上形成塗料之方法，其包含將如請求項1之UV可固化塗料組合物塗佈至該基材之至少一部分。
  7. 一種經塗覆之基材，其包含基材及沈積於該基材之至少一部分上之如請求項1之UV可固化塗料組合物。
  8. 如請求項7之經塗覆之基材，其中該基材包含由以下組成之群形成之基材：聚甲基丙烯酸甲酯、聚碳酸酯及聚對苯二甲酸乙二酯。
  9. 如請求項7或8之經塗覆之基材，其中該基材係適用於機載顯示器、用於電腦及行動電話之PET保護膜及顯示器的基材。
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